Hydroxy addition polymer, anhydride addition polymer and cycloaliphatic polyepoxide

ABSTRACT

Coating compositions which comprise: (i) a hydroxy-functional compound containing in the molecule an average of at least two hydroxyl groups; (ii) an anhydride-functional compound containing in the molecule an average of at least two cyclic carboxylic acid anhydride groups; and (iii) an epoxy-functional compound containing in the molecule an average of at least two cycloaliphatic epoxy groups, provide low temperature cure response and excellent durability.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of copending application Ser. No. 07/120,887filed Nov. 16, 1987, abandoned, which applications is acontinuation-in-part of prior application Ser. No. 06/840,117, filedMar. 14, 1986, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel reactive coatings which can be cured atroom temperature or force dried at temperatures ranging up to about 350°F. The coatings may be utilized as primers, topcoats or as clearcoatsand/or basecoats in clearcoat/basecoat compositions. The combination ofhydroxy-functional compounds, anhydride-functional compounds, andepoxy-functional compounds, especially cycloaliphatic epoxy compounds,provides fast reacting, durable coatings which minimize the toxicityproblems which may be associated with other low temperature curingsystems.

2. Description of the Prior Art

One approach to high performance low temperature curing coatings hasinvolved two component coatings comprising reactive isocyanates andactive hydrogen containing compounds such as hydroxyl containingpolymers or amine containing polymers to produce urethane or ureacoatings. Although these materials have excellent performance and cureat low temperatures, the isocyanates may, under some conditions, berelatively hazardous to handle.

Coating compositions comprising reactive combinations of epoxycontaining compounds and compounds having acid or amine functionalityare known in the art. Similarly, coating compositions comprising cyclicanhydrides and hydroxy-functional compounds are also known in the art.The prior art has not, however, taught the combination ofanhydride-functional compounds, epoxy-functional compounds, andhydroxy-functional compounds to provide low temperature curing coatingshaving excellent durability and performance.

BRIEF SUMMARY OF THE INVENTION

This invention involves a curable composition which comprises: (i) ahydroxy-functional compound having an average of at least two hydroxylgroups per molecule; (ii) an anhydride-functional compound having anaverage of at least two cyclic carboxylic acid anhydride groups permolecule; and (iii) an epoxy-functional compound having an average of atleast one and, preferably, at least two epoxy groups per molecule. Atleast one of the compounds (i), (ii), or (iii) should comprise a filmforming polymer. The term "compound" is used in its broadest sense toinclude monomers, oligomers, and polymers. The term "film formingpolymer" means any polymeric material that can form a film fromevaporation of any carrier or solvent.

In its most preferred formulation, this invention relates to curablecompositions wherein the hydroxy-functional compound is a polymerprepared by the free radical addition polymerization of one or moremonomers, at least one of which contains or can be reacted to produce areactive hydroxyl group; and wherein the anhydride-functional compoundis the addition polymerization product of at least one unsaturatedmonomer having anhydride functionality, especially maleic anhydride, andat least one other ethylenically unsaturated monomer; and wherein theepoxy-functional compound is a cycloaliphatic epoxy compound.

It is especially preferred to utilize the curable composition of thisinvention in combination with from about 5 to about 80%, and especially5 to about 50%, by weight of an inert solvent, such as ketones, esters,and aromatic or aliphatic hydrocarbons. It is convenient to provide thecoating composition as a two-component system wherein theanhydride-functional compound provides one package and thehydroxy-functional compound and the epoxy-functional compound provide asecond package. The two components can be mixed prior to application toprovide the curable coatings.

In one preferred application, this invention relates to coatedsubstrates having a multi-layer decorative and/or protective coatingwhich comprises:

(a) a basecoat comprising a pigmented film-forming polymer; and

(b) a transparent clearcoat comprising a film-forming polymer applied tothe surface of the basecoat composition;

wherein the clearcoat and/or the basecoat comprises the curablecompositions of this invention.

Accordingly, it is an object of this invention to provide improvedcurable compositions having excellent reactivity at low temperatures. Itis a further object of this invention to provide coating compositionswhich may be utilized as primers, topcoats or clearcoats and/orbasecoats in clearcoat/basecoat compositions. Another object of thisinvention is to provide an improved two-component coating compositionwherein one component comprises an anhydride-functional compound and theother component comprises a hydroxy-functional compound and anepoxy-functional compound. Another object of this invention is toprovide coatings having excellent exterior durability and corrosionresistance. A further object of this invention is to provide improvedcoating compositions which can be cured at room temperature or forcedried at elevated temperatures. These and other objects of the inventionwill become apparent from the following discussions.

DETAILED DESCRIPTION OF THE INVENTION

1. HYDROXY-FUNCTIONAL COMPOUNDS

The hydroxy-functional compounds which are useful in the practice ofthis invention have an average of at least two hydroxyl groups permolecule. Although low molecular weight diols and polyols such aspropylene glycol, 1,6-hexanediol triethanol amine, and pentaerythritolcan be utilized in the practice of this invention, it is especiallypreferred to utilize polymeric hydroxy-functional compounds such aspolyethers, polyesters, acrylics, polyurethanes, polycaprolactones, etc.

Preferably the hydroxy-functional polymer will have a number averagemolecular weight of at least about 400. Typical number average molecularweights will range from about 400 to about 30,000, and especially 500 toabout 7,000. In order to provide the fastest rate of reaction duringcure it is preferred in the practice of this invention to utilizehydroxy-functional compounds having predominantly, and preferably all,primary hydroxyl functionality.

Representative hydroxy-functional polymers include those described inSections 1.1 through 1.5 below:

1.1. Polyether polyols are well known in the art and are convenientlyprepared by the reaction of a diol or polyol with the correspondingalkylene oxide. These materials are commercially available and may beprepared by a known process such as, for example, the processesdescribed in Encyclopedia of Chemical Technology, Volume 7, pages257-262, published by Interscience Publishers, Inc., 1951.Representative examples include the polypropylene ether glycols andpolyethylene ether glycols such as those marketed as Niax® Polyols fromUnion Carbide Corporation.

1.2. Another useful class of hydroxy-functional polymers are thoseprepared by condensation polymerization reaction techniques as are wellknown in the art. Representative condensation polymerization reactionsinclude polyesters prepared by the condensation of polyhydric alcoholsand polycarboxylic acids or anhydrides, with or without the inclusion ofdrying oil, semi-drying oil, or non-drying oil fatty acids. By adjustingthe stoichiometry of the alcohols and the acids while maintaining anexcess of hydroxyl groups, hydroxy-functional polyesters can be readilyproduced to provide a wide range of desired molecular weights andperformance characteristics.

The polyester polyols are derived from one or more aromatic and/oraliphatic polycarboxylic acids, the anhydrides thereof, and one or morealiphatic and/or aromatic polyols. The carboxylic acids include thesaturated and unsaturated polycarboxylic acids and the derivativesthereof, such as maleic acid, fumaric acid, succinic acid, adipic acid,azelaic acid, and dicyclopentadiene dicarboxylic acid. The carboxylicacids also include the aromatic polycarboxylic acids, such as phthalicacid, isophthalic acid, terephthalic acid, etc. Anhydrides such asmaleic anhydride, phthalic anhydride, trimellitic anhydride, or NadicMethyl Anhydride (brand name formethylbicyclo[2.2.1]heptene-2,3-dicarboxylic anhydride isomers) can alsobe used.

Representative saturated and unsaturated polyols which can be reacted instoichiometric excess with the carboxylic acids to producehydroxy-functional polyesters include diols such as ethylene glycol,dipropylene glycol, 2,2,4-trimethyl 1,3-pentanediol, neopentyl glycol,1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol,1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol,1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-bis(2-hydroxyethoxy)cyclohexane,trimethylene glycol, tetramethylene glycol, pentamethylene glycol,hexamethylene glycol, decamethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, norbornylene glycol,1,4-benzenedimethanol, 1,4-benzenediethanol,2,4-dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, and polyolssuch as trimethylolethane, trimethylolpropane, trimethylolhexane,triethylolpropane, 1,2,4-butanetriol, glycerol, pentaerythritol,dipentaerythritol, etc.

Typically, the reaction between the polyols and the polycarboxylic acidsis conducted at about 120° C. to about 200° C. in the presence of anesterification catalyst such as dibutyl tin oxide.

1.3. Additionally, hydroxy-functional polymers can be prepared by thering opening reaction of epoxides and/or polyepoxides with primary or,preferably, secondary amines or polyamines to produce hydroxy-functionalpolymers. Representative amines and polyamines include ethanol amine,N-methylethanol amine, dimethyl amine, ethylene diamine, isophoronediamine, etc. Representative polyepoxides include those prepared bycondensing a polyhydric alcohol or polyhydric phenol with anepihalohydrin, such as epichlorohydrin, usually under alkalineconditions. Some of these condensation products are availablecommercially under the designations EPON or DRH from Shell ChemicalCompany, and methods of preparation are representatively taught in U.S.Pat. Nos. 2,592,560; 2,582,985 and 2,694,694.

1.4. Other useful hydroxy-functional polymers can be prepared by thereaction of at least one polyol, such as those representativelydescribed in Section 1.2 above, with polyisocyanates to producehydroxy-functional urethanes. Representative polyisocyanates having twoor more isocyanate groups per molecule include the aliphatic compoundssuch as ethylene, trimethylene, tetramethylene, pentamethylene,hexamethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene, 1,3-butylene,ethylidene and butylidene diisocyanates; the cycloalkylene compoundssuch as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, and the1,3-cyclopentane, 1,3-cyclohexane, and 1,2-cyclohexane diisocyanates;the aromatic compounds such as m-phenylene, p-phenylene, 4,4'-diphenyl,1,5-naphthalene and 1,4-naphthalene diisocyanates; thealiphatic-aromatic compounds such as 4,4'-diphenylene methane, 2,4- or2,6-toluene, or mixtures thereof, 4,4'-toluidine, and 1,4-xylylenediisocyanates; the nuclear substituted aromatic compounds such asdianisidine diisocyanate, 4,4'-diphenylether diisocyanate andchlorodiphenylene diisocyanate; the triisocyanates such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanate benzene and2,4,6-triisocyanate toluene; and the tetraisocyanates such as4,4'-diphenyl-dimethyl methane-2,2'-5,5'-tetraisocyanate; thepolymerized polyisocyanates such as tolylene diisocyanate dimers andtrimers, and other various polyisocyanates containing biuret, urethane,and/or allophanate linkages. The polyisocyanates and the polyols aretypically reacted at temperatures of 25° C. to about 150° C. to form thehydroxy-functional polymers.

1.5. Useful hydroxy-functional polymers can also be convenientlyprepared by free radical polymerization techniques such as in theproduction of acrylic resins. The polymers are typically prepared by theaddition polymerization of one or more monomers. At least one of themonomers will contain, or can be reacted to produce, a reactive hydroxylgroup. Representative hydroxy-functional monomers include 2-hydroxyethylacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate,2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 4-hydroxypentylacrylate, 2-hydroxyethyl ethacrylate, 3-hydroxybutyl methacrylate,2-hydroxyethyl chloroacrylate, diethylene glycol methacrylate,tetraethylene glycol acrylate, para-vinyl benzyl alcohol, etc. Typicallythe hydroxy-functional monomers would be copolymerized with one or moremonomers having ethylenic unsaturation such as:

(i) esters of acrylic, methacrylic, crotonic, tiglic, or otherunsaturated acids such as: methyl acrylate, ethyl acrylate, propylacrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate,ethylhexyl acrylate, amyl acrylate, 3,5,5-trimethylhexyl acrylate,methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobornylmethacrylate, dimethylaminoethyl methacrylate, ethyl tiglate, methylcrotonate, ethyl crotonate, etc.;

(ii) vinyl compounds such as vinyl acetate, vinyl propionate, vinylbutyrate, vinyl isobutyrate, vinyl benzoate, vinyl m-chlorobenzoate,vinyl p-methoxybenzoate, vinyl alpha-chloroacetate, vinyl toluene, vinylchloride, etc.;

(iii) styrene-based materials such as styrene, alpha-methyl styrene,alpha-ethyl styrene, alpha-bromo styrene, 2,6-dichlorostyrene, etc.;

(iv) allyl compounds such as allyl chloride, allyl acetate, allylbenzoate, allyl methacrylate, etc.;

(v) other copolymerizable unsaturated monomers such as acrylonitrile,methacrylonitrile, dimethyl maleate, isopropenyl acetate, isopropenylisobutyrate, acrylamide, methacrylamide, and dienes such as1,3-butadiene, etc.

The polymers are conveniently prepared by conventional free radicaladdition polymerization techniques. Frequently, the polymerization willbe initialized by conventional initiators known in the art to generate afree radical such as azobis(isobutyronitrile), cumene hydroperoxide,t-butyl perbenzoate, etc. Typically, the acrylic monomers are heated inthe presence of the initiator at temperatures ranging from about 35° C.to about 200° C., and especially 75° C. to 150° C., to effect thepolymerization. The molecular weight of the polymer can be controlled,if desired, by the monomer selection, reaction temperature and time,and/or the use of chain transfer agents as is well known in the art.

Especially preferred in the practice of this invention arehydroxy-functional polyesters and hydroxy-functional acrylic polymers.An especially preferred hydroxy-functional polymer is the additionpolymerization reaction product of (a) 10 to about 40 weight percent ofa hydroxy-functional ethylenically unsaturated monomer and (b) 60 toabout 90 weight percent of at least one ethylenically unsaturatedmonomer copolymerizable with the hydroxy-functional monomer.

2. ANHYDRIDE-FUNCTIONAL COMPOUNDS

The anhydride-functional compounds which are useful in the practice ofthis invention can be any aliphatic or aromatic compound having at leasttwo cyclic carboxylic acid anhydride groups in the molecule. Polymericanhydrides having number average molecular weights between 500 and 7,000are most useful. Especially preferred in the practice of this inventionis the use of free radical addition polymers, such as acrylic polymers,having anhydride functionality. These are conveniently prepared as iswell known in the art by polymerizing an unsaturated monomer havinganhydride functionality, such as maleic anhydride, citraconic anhydride,itaconic anhydride, propenyl succinic anhydride, etc. with otherethylenically unsaturated monomers such as the esters of unsaturatedacids, vinyl compounds, styrene-based materials, allyl compounds andother copolymerizable monomers, all as representatively taught inSection 1.5. of this specification and also may include, aspolymerizable monomers, unsaturated acids.

For some applications, it is preferred to utilize ananhydride-functional polymer which has no free carboxylic acid groups onthe anhydride-functional polymer. Surprisingly, however, theincorporation of relatively small amounts, e.g. less than about 15% ofthe total polymer weight, of an unsaturated monomer having freecarboxylic acid groups, e.g. acrylic acid, methacrylic acid, tiglicacid, crotonic acid, maleic acid, etc., can provide improved color andextended stability and pot-life in certain formulations, especiallythose incorporating amines as catalysts. Therefore, one preferredapproach to the formulation of the anhydride-functional compoundsinvolves those prepared by the addition polymerization of at least oneunsaturated monomer having anhydride functionality, at least oneunsaturated monomer having free carboxylic acid functionality, and,optionally, at least one other ethylenically unsaturated copolymerizablemonomer.

The monomers which are copolymerized with the unsaturated anhydrideshould, of course, be free of any functionality which could react withthe anhydride group during the polymerization. The anhydride-functionaladdition polymers can be conveniently prepared by conventional freeradical addition polymerization techniques. Typically the polymerizationwill be conducted in an inert solvent and in the presence of aninitiator at temperatures ranging from 35° C. to about 200° C. Anespecially preferred anhydride-functional vehicle comprises the freeradical addition polymerization product of (a) 5 to 40, and especially15 to about 25, weight percent of an ethylenically unsaturatedmonoanhydride and (b) 60 to 95, and especially 75 to about 85, weightpercent of at least one other ethylenically unsaturated monomercopolymerizable with the ethylenically unsaturated anhydride.

Another especially preferred anhydride-functional polymeric vehiclecomprises the free radical addition product of:

(a) 5 to about 40, and especially 15 to about 25, weight percent of anethylenically unsaturated mono-anhydride monomer; and

(b) 1 to about 15 weight percent of an ethylenically unsaturatedcarboxylic acid monomer copolymerizable with the ethylenicallyunsaturated monoanhydride; and

(c) 45 to about 94 weight percent of at least one ethylenicallyunsaturated monomer which is copolymerizable with the ethylenicallyunsaturated monoanhydride and ethylenically unsaturated acid.

Surprisingly, it has been found that anhydride-functional polymersincorporating acrylate monomers, such as acrylic acid, butyl acrylate,etc. frequently provide a darker color polymer when used in combinationwith the preferred amine catalysts, e.g. imidazoles, of this inventionthan similar polymers using the corresponding methacrylate monomers suchas methacrylic acid, butyl methacrylate, etc. Therefore, in those caseswhere color development may be critical it is preferred to minimize theamount of acrylate monomer, e.g. from 0 to not more than about 10 weightpercent of the total monomer mixture. Especially preferred to minimizecolor development are anhydride-functional free radical additionpolymers which are the polymerization product of monomers which are freeof acrylate groups. These monomers may, of course, contain methacrylatefunctionality or other α-β-unsaturated carbonyl functionality where theα carbon is not directly bonded to a hydrogen atom.

Other polyanhydrides, in addition to the anhydride-functional additionpolymerization products, can also be utilized in the practice of thisinvention. Ester anhydrides can be prepared, as is known in the art, bythe reaction of e.g. trimellitic anhydride with polyols. Otherrepresentative, suitable polyanhydrides include poly-functional cyclicdianhydrides such as cyclopentane tetracarboxylic acid dianhydride,diphenyl-ether tetracarboxylic acid dianhydride, 1,2,3,4,-butanetetracarboxylic acid dianhydride, and the benzophenone tetracarboxylicdianhydrides such as 3,3',4,4'-benzophenone tetracarboxylic dianhydride,and 2,bromo-3,3',4,4'-benzophenone tetracarboxylic acid dianhydride.Trianhydrides such as the benzene and cyclohexene hexacarboxylic acidtrianhydrides are also useful.

Additionally, useful polyanhydrides can be prepared by the maleinizationof polyunsaturated compounds such as unsaturated rubbers, unsaturatedoils and unsaturated hydrocarbons.

3. EPOXY-FUNCTIONAL COMPOUNDS

The coatings of this invention also require the use of at least oneepoxy-functional compound. The epoxy compounds can be monoepoxies, or,preferably, a polyepoxide having an average of at least two epoxy groupsper molecule.

Representative useful monoepoxides include the monoglycidyl ethers ofaliphatic or aromatic alcohols such as butyl glycidyl ether, octylglycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, dodecylglycidyl ether, p-tert-butylphenyl glycidyl ether, and o-cresyl glycidylether. Monoepoxy esters such as the glycidyl ester of versatic acid(commercially available as CARDURA® E from Shell Chemical Company), orthe glycidyl esters of other acids such as tertiary-nonanoic acid,tertiary-decanoic acid, tertiary-undecanoic acid, etc. are also useful.Similarly, if desired, unsaturated monoepoxy esters such as glycidylacrylate, glycidyl methacrylate or glycidyl laurate could be used.Additionally, monoepoxidized oils can also be used.

Other useful monoepoxies include styrene oxide, cyclohexene oxide,1,2-butene oxide, 2,3-butene oxide, 1,2-pentene oxide, 1,2-hepteneoxide, 1,2-octene oxide, 1,2-nonene oxide, 1,2-decene oxide, and thelike.

It is only necessary that the monoepoxide compounds have a sufficientlylow volatility to remain in the coating composition under the applicableconditions of cure.

Polyepoxides are especially preferred in the reactive coatings of thisinvention. Especially preferred as the poly-functional epoxy compounds,due to their reactivity and durability, are the polyepoxy-functionalcycloaliphatic epoxies. Preferably, the cycloaliphatic epoxies will havea number average molecular weight less than about 2,000 to minimize theviscosity. The cycloaliphatic epoxies are conveniently prepared bymethods well known in the art such as epoxidation of dienes or polyenes,or the epoxidation of unsaturated esters by reaction with a peracid suchas peracetic and/or performic acid.

Commercial examples of representative preferred cycloaliphatic epoxiesinclude 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g."ERL-4221" from Union Carbide Corp.);bis(3,4-epoxycyclohexylmethyl)adipate (e.g. "ERL-4299" from UnionCarbide Corporation); 3,4-epoxy-6-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexane carboxylate (e.g. "ERL-4201" from UnionCarbide Corp.); bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (e.g."ERL-4289" from Union Carbide Corp.); bis(2,3-epoxycyclopentyl) ether(e.g. "ERL-0400" from Union Carbide Corp.); dipentene dioxide (e.g."ERL-4269" from Union Carbide Corp.);2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane (e.g."ERL-4234" from Union Carbide Corp.). Other commercially availablecycloaliphatic epoxies are available from Ciba-Geigy Corporation such asCY 192, a cycloaliphatic diglycidyl ester epoxy resin having an epoxyequivalent weight of about 154. The manufacture of representativecycloaliphatic epoxies is taught in various patents including U.S. Pat.Nos. 2,884,408, 3,027,357 and 3,247,144.

Other polyepoxides potentially useful in the practices of this inventioninclude aliphatic and aromatic polyepoxies, such as those prepared bythe reaction of an aliphatic polyol or polyhydric phenol and anepihalohydrin. Other useful epoxies include epoxidized oils and acrylicpolymers derived from ethylenically unsaturated epoxy-functionalmonomers such as glycidyl acrylate or glycidyl methacrylate incombination with other copolymerizable monomers such as those listed in1.5 above.

Since hydroxyl functionality is already available in the reactivecoatings from the hydroxy-functional compounds of this invention, it isoften desirable to utilize epoxy-functional compounds which aresubstantially free of hydroxyl groups. The ratios of anhydride tohydroxyl to epoxy groups can be widely varied within the practice ofthis invention as long as at least some amount of each of theanhydride-functional compound, the hydroxy-functional compound and theepoxy-functional compound are present in the coating mixture. It isespecially preferred, however, to provide 0.3 to about 6.0 hydroxylgroups and about 0.3 to about 6.0 epoxy groups for each anhydride groupin the reactive system. It is especially preferred to provide 0.5 to 1.5hydroxyl groups and 0.5 to 1.5 epoxy groups for each anhydride group. Atleast one of the hydroxy-functional compound, the epoxy-functionalcompound, or the anhydride-functional compound should be a film formingpolymer, and each of the compounds should be mutually soluble with theother compounds.

The coatings of this invention can be cured at temperatures ranging fromabout room temperature up to about 350° F. The coatings can be used asclear coatings or they may contain pigments as is well known in the art.Representative opacifying pigments include white pigments such astitanium dioxide, zinc oxide, antimony oxide, etc. and organic orinorganic chromatic pigments such as iron oxide, carbon black,phthalocyanine blue, etc. The coatings may also contain extenderpigments such as calcium carbonate, clay, silica, talc, etc.

The coatings may also contain other additives such as flow agents,catalysts, diluents, solvents, ultraviolet light absorbers, etc.

It is especially preferred in the practice of this invention to includea catalyst for the reaction of anhydride groups and hydroxyl groups andalso a catalyst for the reaction of epoxy and acid groups. It isespecially preferred in the practice of this invention to utilizetertiary amines and especially N-methylimidazole as a catalyst for theanhydride/hydroxyl reaction. The catalyst for the anhydride/hydroxylreaction will typically be present at a level of at least 0.01% byweight of the anhydride compound and preferably 1.0 to about 5.0%.

Tertiary amines, secondary amines such as ethyl imidazole, quaternaryammonium salts, nucleophilic catalysts, such as lithium iodide,phosphonium salts, and phosphines such as triphenyl phosphine areespecially useful as catalysts for epoxy/acid reactions. Electrophilliccatalysts, such as tin metal salts or complexes, are also useful in thepractice of this invention. The catalyst for the epoxy/acid reactionwill typically be present at a level of at least 0.01% by weight of thetotal acid-functional compound and epoxy-functional compound and,preferably, will be present at 0.1 to about 3.0%.

The coatings of this invention may typically be applied to any substratesuch metal, plastic, wood, glass, synthetic fibers, etc. by brushing,dipping, roll coating, flow coating, spraying or other methodconventionally employed in the coating industry. If desired, thesubstrates may be primed prior to application of the coatings of thisinvention.

One preferred application of the curable coatings of this inventionrelates to their use as clearcoats in clearcoat/basecoat formulations.

Clearcoat/basecoat systems are well known, especially in the automobileindustry where it is especially useful to apply a pigmented basecoat,which may contain metallic pigments, to a substrate and allow it to forma polymer film followed by the application of a clearcoat which will notmix with or have any appreciable solvent attack upon the previouslyapplied basecoat. The basecoat composition may be any of the polymersknown to be useful in coating compositions including the reactivecompositions of this invention.

One useful polymer basecoat includes the acrylic addition polymers,particularly polymers or copolymers of one or more alkyl esters ofacrylic acid or methacrylic acid, optionally together with one or moreother ethylenically unsaturated monomers. These polymers may be ofeither the thermoplastic type or the thermosetting, crosslinking typewhich contain hydroxyl or amine or other reactive functionality whichcan be crosslinked. Suitable acrylic esters and unsaturated monomers foreither type of polymer include methyl methacrylate, ethyl methacrylate,propyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate,vinyl acetate, acrylonitrile, acrylamide, styrene, vinyl chloride, etc.Where the polymers are required to be of the crosslinking type, suitablefunctional monomers which can be used in addition to those alreadymentioned include acrylic or methacrylic acid, hydroxy ethyl acrylate,2-hydroxy propyl methacrylate, glycidyl acrylate, tertiary-butyl aminoethyl methacrylate, etc. The basecoat composition may, in such a case,also contain a crosslinking agent such as a polyisocyanate, apolyepoxide, or a nitrogen resin such as a condensate of an aldehydesuch as formaldehyde with a nitrogeneous compound such as urea, melamineor benzoguanamine or a lower alkyl ether of such a condensate. Otherpolymers useful in the basecoat composition include vinyl copolymerssuch as copolymers of vinyl esters of inorganic or organic acids, suchas vinyl chloride, vinyl acetate, vinyl propionate, etc., whichcopolymers may optionally be partially hydrolyzed so as to introducevinyl alcohol units.

Other polymers useful in the manufacture of the basecoat include alkydresins or polyesters which can be prepared in a known manner by thecondensation of polyhydric alcohols and polycarboxylic acids, with orwithout the inclusion of natural drying oil fatty acids as describedelsewhere in this specification. The polyesters or alkyds may contain aproportion of free hydroxyl and/or carboxyl groups which are availablefor reaction, if desired with suitable crosslinking agents as discussedabove.

If desired, the basecoat composition may also contain minor amounts of acellulose ester, to alter the drying or viscosity characteristics of thebasecoat.

Typically, the basecoat will include pigments conventionally used forcoating compositions and after being applied to a substrate, which mayor may not previously have been primed, the basecoat will be allowedsufficient time to form a polymer film which will not be lifted duringthe application of the clearcoat. The basecoat may be heated or merelyallowed to air-dry to form the film. Generally, the basecoat will beallowed to dry for about 1 to 20 minutes before application of theclearcoat. The clearcoat is then applied to the surface of the basecoat,and the system can be allowed to dry at room temperature or, if desired,can be force dried by baking the coated substrate at temperaturestypically ranging up to about 350° F.

Typically, the clearcoat may contain ultraviolet light absorbers such ashindered phenols or hindered amines at a level ranging up to about 6% byweight of the vehicle solids as is well known in the art. The clearcoatcan be applied by any application method known in the art, butpreferably will be spray applied. If desired, multiple layers ofbasecoat and/or clearcoat can be applied. Typically, both the basecoatand the clearcoat will each be applied to give a dry film thickness ofabout 0.01 to about 6, and especially about 0.5 to about 3.0 mils.

If desired, the novel reactive compositions taught herein could be usedas a basecoat, in which case the clearcoat could also comprise the novelreactive coatings taught herein, or the polymers taught herein as beinguseful as basecoat formulations could be utilized as clearcoats.

The following examples have been selected to illustrate specificembodiments and practices of advantage to a more complete understandingof the invention. Unless otherwise stated, "parts" means parts-by-weightand "percent" is percent-by-weight. The numeric ratings for solventresistance (MEK rubs), wet adhesion, and salt spray are on a scale of0-10, 10 best.

In each of the clearcoat/basecoat formulations described in Examples 14through 24 the primer was G.B.P.® etching primer filler (2-componentvinyl-butyral based primer commercially available from TheSherwin-Williams Company) and the basecoat was Acrylyd® acrylic enamel(a lacquer-like coating commercially available from The Sherwin-WilliamsCompany). In each of the clearcoat/basecoat formulations described inExamples 31-35 the primer was a thermoplastic lacquer primer/sealer(commercially available from The Sherwin-Williams Company as AcrylicGray Sealer P1A38) and the basecoat was Acrylyd® acrylic enamel F5S112(a lacquer-like aluminum pigmented basecoat commercially from TheSherwin-Williams Company). The primer, the basecoat and the clearcoatwere applied to provide dry film thicknesses of 1.0, 1.0 and 2.0 milsrespectively.

The following examples have been selected to illustrate specificembodiments and practices of advantage to a more complete understandingof the invention. Unless otherwise stated "parts" means parts by weightand percent is percent by weight.

EXAMPLE 1

A four neck, round bottom reaction flask equipped with nitrogen inlet,condenser, mechanical stirrer, and fluid metering pump was charged with4,000 parts methyl amyl ketone and heated to reflux. A monomer mix of600 parts hydroxy ethyl acrylate, 1,500 parts butyl acrylate, 2,100parts styrene, 600 parts methyl methacrylate, 1,200 parts Tone™ M-100(hydroxy-functional acrylic monomer produced by Union CarbideCorporation having a molecular weight of about 344 and believed to bethe reaction product of one mole of 2-hydroxyethyl acrylate with 2 molesof ε-caprolactone), 210 parts Vazo-67 (initiator sold by E.I. duPontbelieved to be 2,2'-azobis(2-methylbutyronitrile)), 55.6 parts3-mercapto propanol, and a subsequent addition of 64.4 parts 3-mercaptopropanol were charged over a period of three hours under a nitrogenblanket while maintaining reflux temperature.

The mixture was maintained at reflux temperature until the resultantresin had a percent solids of approximately 56.4% (94% conversion). Theresin was then solvent stripped under vacuum to 80% solids by weight.

EXAMPLE 2

In like manner to Example 1, a hydroxy-functional acrylic polymer wasprepared by charging a reaction vessel with 279.54 parts aromatic napthawhich was heated to about 320° F. A monomer mixture comprising 137.64parts styrene, 130.54 parts methyl methylacrylate, 196.91 parts butylacrylate and 186.15 parts hydroxyethyl methacrylate, was charged intothe reaction vessel at a uniform rate over about five hours.Simultaneously with the addition of the monomer mixture, a mixture of28.62 parts t-butyl perbenzoate in 40.60 parts aromatic naptha was alsoadded to the reaction vessel. The reaction mixture was then maintainedat about 320° F. for about 90 minutes at which point the resultant resinhad a percent solids of approximately 68%.

EXAMPLE 3

An anhydride-functional acrylic polymer was prepared by charging 694.4parts of maleic anhydride and 2777.8 parts of xylene into a four neckreaction flask equipped with a nitrogen inlet, mechanical stirrer, watertrap, condenser and fluid metering pump. The mixture was then heated toreflux, and a monomer mixture comprising 2777.8 parts butyl acrylate,2777.8 parts methyl methacrylate, 694.4 parts maleic anhydride, and 158parts t-butyl perbenzoate was charged into the reaction flask over aperiod of three hours under a nitrogen blanket while maintaining refluxtemperature. The mixture was maintained at that temperature for about 15minutes at which point a mixture of 30.9 parts t-butyl perbenzoate in277.8 parts xylene was charged over a period of 45 minutes. The reactionmixture was then maintained at reflux temperatures for about two hours.The resulting anhydride-functional resin was about 71% solids by weight,and had an acid value of 113.2.

EXAMPLE 4

In like manner to Example 3 an anhydride-functional resin comprising 20%maleic anhydride, 20% isobutyl methacrylate, 30% butyl acrylate, and 30%methyl methacrylate was prepared as a 91% solid solution in xylene.

EXAMPLES 5-10

Clear coatings were prepared by admixing anhydride-functional vehicles,hydroxyl-functional vehicles and epoxy-functional vehicles according tothe following formulations:

    __________________________________________________________________________           HYDROXYL                                                                              ANHYDRIDE                                                                             EPOXY   RATIO OF ANHYDRIDE/                            EXAMPLE                                                                              COMPOUND                                                                              COMPOUND                                                                              COMPOUND                                                                              HYDROXYL/EPOXY GROUPS                          __________________________________________________________________________    5      EX. 1   EX. 3   NONE    1/1/0                                          6      "       "       ERL 4299.sup.1                                                                          2/1/1.25                                     7      "       "       "         2/1/1.5                                      8      "       "       "       2/1/2                                          9      EX. 2   "       "         2/1/1.5                                      10     "       EX. 4   "       1/1/1                                          __________________________________________________________________________     .sup.1 bis(3,4epoxycyclohexylmethyl)adipate from Union Carbide                Corporation.                                                             

Each of the coatings were catalyzed at approximately 3.5%N-methylimidazole (based on anhydride compound solids) and eachformulation was reduced with xylene to an appropriate applicationviscosity and then spray applied over Bonderite® 1000 treated steelpanels. The coatings gave the following test results:

    ______________________________________                                                  EXAMPLE                                                                       5    6       7      8    9     10                                   ______________________________________                                        Tack Free Time                                                                            6      7       8    18   --    --                                 (hrs.)                                                                        Cure (MEK rubs).sup.1                                                         air dry (1 day)                                                                           0      3       2     3   1     1                                  air dry (11 days)                                                                         0      8       8     9   5     5                                  air dry (28 days)                                                                         9      9       9     9   5     7                                  Humidity Resis-                                                                           10     10      10   10   10    10                                 tance.sup.1,2                                                                 (170 hours)                                                                   Salt Spray.sup.1,2                                                                        8      8       10   10   10    9                                  Knoop Hardness                                                                            40     88      89   87   103   96                                 Number.sup.2                                                                  Cure (MEK   5      9       9     9   --    --                                 rubs).sup.1,3                                                                 Knoop Hardness                                                                            42     86      88   78   --    --                                 Number.sup.3                                                                  Cure (MEK   3      9       9    10   --    --                                 rubs).sup.1,4                                                                 Knoop Hardness                                                                            39     94      96   80   --    --                                 Number.sup.4                                                                  ______________________________________                                         .sup.1 scale of 1-10 with 10 being highest                                    .sup.2 after air dry for 28 days                                              .sup.3 after 180°  F. bake for 30 minutes                              .sup.4 after 250° F. bake for 30 minutes                          

As shown in these results, the addition of the epoxy compound improvescure and hardness performance as opposed to similar formulations withoutepoxy. All of the Example formulations showed excellent clarity.

EXAMPLE 11

A hydroxyl-functional polymer was prepared by charging a polymerizationreactor equipped with a mechanical stirrer, a water cooled condenser,nitrogen inlet, water trap, thermometer, heating mantle and fluidmetering pump with 172.5 parts of n-butyl acetate. The reaction vesselwas heated to approximately 237° F. and a monomer premix composed of96.2 parts of methyl methacrylate, 63.0 parts of butyl acrylate, 58parts of hydroxy ethyl methacrylate, 54 parts styrene and an initiatorpremixture composed of 11.5 parts of n-butyl acetate and 5.7 parts ofVazo 67 was metered simultaneously into the polymerization reactor at aconstant rate over approximately 4 hours. The reaction temperature wasmaintained for an additional 2 hours after the addition was completedand cooled for one hour. The resulting hydroxy-functional polymer had anumber average molecular weight of approximately 9,600.

EXAMPLE 12

A 4 neck, round bottomed flask equipped with mechanical stirrer, refluxcondenser, thermometer, nitrogen inlet and fluid metering pump wascharged with 1472 parts xylene, 240 parts maleic anhydride and heated toreflux (139° C.) under nitrogen. A monomer mixture of 480 parts isobutylmethacrylate, 720 parts butyl acrylate, 720 parts methyl methacrylate,120 parts maleic anhydride and 60 parts t-butyl perbenzoate were thenmetered into the reaction over a 3-hour period. Halfway through theaddition, an additional 120 parts of maleic anhydride was charged to thereaction vessel and monomer addition was continued. After refluxing thereaction mixture for an additional 15 minutes, 12 parts of t-butylperbenzoate in 128 parts xylene were added over 45 minutes. Heating wascontinued for 2 hours at reflux. The resulting xylene solubleanhydride-functional resin was 61.2% solids, had a Gardner Holdtviscosity of 24.5, an acid value of 116.5, and a density ofapproximately 8.6 pounds per gallon.

EXAMPLE 13

A reaction vessel equipped as in Example I was charged with 6,624 partsof xylene, 648 parts of maleic anhydride and heated to reflux undernitrogen. To this heated solution a monomer mixture of 5,616 parts butylacrylate, 3,024 parts methylmethacrylate, 540 parts maleic anhydride and270 parts of t-butyl peroctoate was metered into the reaction vessel ata constant rate over a 3-hour time period. At 1 hour and at 2 hours intothe monomer addition, heating and monomer addition were stopped and thereactor was charged with 540 parts and 432 parts of maleic anhydriderespectively. Heating was resumed to reflux and the monomer addition wascontinued. The reaction mixture was maintained at reflux temperature foran additional 15 minutes after the completion of all of the monomeraddition. A solution of 54 parts of t-butyl peroctoate in 576 partsxylene was added to the reaction over a 45-minute period. The reactionwas held at reflux for an additional 2 hours and then allowed to cool toroom temperature to obtain an anhydride-functional polymer having anumber average molecular weight of about 1,800 and a free maleicanhydride content of less than 0.1%. This polymer had an average ofabout 3.6 anhydride groups per molecule.

EXAMPLE 14

A curable clear coating intended for use over a basecoat/primer systemwas prepared according to the following recipe:

    ______________________________________                                        Raw Materials              Parts                                              ______________________________________                                        Hydroxy-Functional Polymer of Example 11                                                                 346.17                                             Anhydride-Functional Polymer of Example 12                                                               187.21                                             ERL 4221                   47.89                                              Xylene                     184.71                                             BYK 300                    2.5                                                20% N-methylimidazole/Methyl Isobutyl Ketone                                                             19.98                                              20% Triphenylphosphine/Toluene                                                                           5.25                                               20% Tinuvin 328/Toluene    23.42                                              Tinuvin 292                2.81                                               ______________________________________                                    

This coating formulation represents approximately 1.5 hydroxyl groupsand 1.5 epoxy groups per each anhydride group. The N-methylimidazolecatalyst was present at approximately 3.5% based on anhydride solids.The triphenylphosphine catalyst was present at approximately 1% basedupon epoxy solids. This coating was reduced with suitable solvents andspray applied over a basecoat/primer system on iron phosphate treatedcold rolled steel. This coating system was allowed to ambient cure 24hours before testing.

The resultant film exhibited a Konig Pendulum Hardness of 14 after oneday, 32 after one week and 52 after four weeks. The coating exhibited asolvent resistance (MEK rubs) rating of 9 after one day. A wet adhesionrating of 8 was obtained immediately after one week exposure tohumidity.

EXAMPLES 15-24

Examples 15-24 were carried out by a similar procedure to that describedfor Example 14 except for the modifications described in the tablebelow. The anhydride-functional polymer used in Examples 15-24 is thatof Example 13. The properties listed in the table below illustrate theeffects of various coating formulations.

    __________________________________________________________________________    Example     15  16  17  18  19  20  21  22  23  24                            __________________________________________________________________________    Component Equivalents                                                         Epoxy       .33 1   3   .5  1   2   1   .56 1   1.75                          Hydroxyl    .33 3   1   1   .5  2   1   .56 1.75                                                                              1                             Anhydride   1   1   1   1   1   1   1   1   1   1                             Konig Pendulum                                                                            69  56  39  68  74  56  69  73  69  66                            hardness (3 weeks)                                                            MEK Rubs (3 weeks)                                                                        6   5   9   7   9   7   7   7   7-  9                             20° Gloss                                                                          52  81  78  77  78  81  78  74  79  81                            Dry Film Thickness                                                                        3.5 3.8 3.1 3.5 3.2 3.4 3.5 3.5 3.5 3.5                           (mils)                                                                        Humidity                                                                      Init 20° Gloss                                                                     53  85  82  79  79  85  79  77  83  84                            Final 20° Gloss                                                                    53  73  48  68  66  78  68  65  75  73                            % Retention 100 86  59  86  84  92  86  84  90  87                            Wet Adhesion                                                                              9+  10  8   10  10  10  10  10  10  9+                            Blushing     5  8   5   9   9   7   7   7   7   6                             Salt Spray  10  9   9   9   8   10- 8   10  9   9                             Scribe Corrosion                                                              Wet Adhesion                                                                              10  10  10  10  10  10  10  10  10  10                            Scribe Blister                                                                            NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                                                                              NONE                          __________________________________________________________________________

EXAMPLE 25

A 4-neck, round bottomed flask equipped with mechanical stirrer, refluxcondenser, thermometer, nitrogen inlet, water trap and fluid meteringpump was charged with 1,280 parts xylene, 170.2 parts maleic anhydrideand heated to reflux (139° C.) under nitrogen for a period of 15 minutesto remove water. The reaction mixture was cooled to 120° C. To thissolution was added a monomer mixture of 591.6 parts isobutylmethacrylate, 918 parts butyl methacrylate, 122.4 parts methacrylicacid, 102 parts maleic anhydride and 61.2 parts t-butyl peroctoate thatwas metered into the reaction vessel at a constant rate over 3 hours.Halfway through the monomer addition, 135.8 parts of maleic anhydridewas charged. The reaction mixture was maintained at 120° C. for anadditional 15 minutes after the completion of all of the monomeraddition. A solution of 80 parts xylene and 10.2 parts t-butylperoctoate was added to the reaction over a 45 minute period. Thereaction was held for 11/2 hours at 120° C., heated to reflux (136° C.)for 1/2 hour to remove water and then the product was cut to 50%theoretical NVM by the addition of 680 parts xylene. The reactionmixture was allowed to cool to room temperature to obtain ananhydride-functional polymer having an average molecular weight of about4,000, a polydispersity of 2.3, and a theoretical anhydride equivalentweight of 490.

EXAMPLE 26

A 4-neck, round bottomed flask equipped with mechanical stirrer, refluxcondenser, thermometer, nitrogen inlet, water trap and fluid meteringpump was charged with 1,472 parts xylene, 168 parts maleic anhydride andheated to reflux (139° C.) under nitrogen. A monomer mixture of 960parts methyl methacrylate, 192 parts butyl acrylate, 768 parts isobutylmethacrylate, 120 parts maleic anhydride and 60 parts t-butylperbenzoate were metered at a constant rate into the reaction vesselover a 3 hour time period. At 1 and 2 hours into the monomer additionthe heating and monomer addition were stopped and an additional 120parts and 72 parts, respectively of maleic anhydride was charged to thereaction vessel. Heating was resumed to reflux and the monomer additionwas continued. The reaction mixture was maintained at reflux for anadditional 15 minutes after the completion of all of the monomeraddition. A solution of 12 parts t-butyl perbenzoate in 128 parts xylenewas added to the reaction over a 45 minute time period. The reaction washeld at reflux for an additional 2 hours and then allowed to cool toroom temperature to obtain an anhydride-functional polymer having anumber average molecular weight of 2,400 and a polydispersity of 2.1.

EXAMPLE 27

A 4-neck, round bottomed flask equipped with mechanical stirrer, refluxcondenser, thermometer, nitrogen inlet, water trap and fluid meteringpump was charged with 1,634 parts xylene, 264 parts maleic anhydride andheated to reflux (139° C.) under nitrogen. To this heated solution, amonomer mixture of 1,372.8 parts butyl methacrylate, 739.2 parts laurylmethacrylate, 132 parts maleic anhydride and 59.4 parts t-butylperoctoate was metered into the reaction vessel at a constant rate overa 21/2 hour time period. Halfway through the monomer addition, heatingand monomer addition were stopped and the reactor was charged with 132parts of maleic anhydride. Heating was resumed to reflux and the monomeraddition was continued. The reaction mixture was maintained at refluxtemperature for an additional 15 minutes after the completion of themonomer addition. A solution of 13.2 parts t-butyl peroctoate and 126parts xylene was added to the reaction over a 45 minute time period. Thereaction was held at reflux for an additional 2 hours and then allowedto cool to room temperature to obtain an anhydride-functional polymerhaving a number average molecular weight of 3,200, a polydispersity of2.1, and a theoretical anhydride equivalent weight of 490.

EXAMPLE 28

A 4-neck, round bottomed flask equipped with mechanical stirrer, refluxcondenser, thermometer, nitrogen inlet, water trap and fluid meteringpump was charged with 1,660 parts xylene, 264 parts maleic anhydride andheated to reflux (139° C.) under nitrogen. A monomer mixture of 1,372.8parts butyl acrylate, 507.4 parts methyl methacrylate, 231.8 partsmethacrylic acid, 132 parts maleic anhydride and 59.4 parts t-butylperoctoate were metered at a constant rate into the reaction over a 21/2hour period. Halfway through the monomer addition, heating and monomeraddition were stopped and an additional 132 parts of maleic anhydridewas charged to the reaction vessel. Heating was resumed to reflux, andthe monomer addition was continued. The reaction mixture was maintainedat reflux temperature for an additional 15 minutes after the completionof all the monomer addition. A solution of 13.2 parts t-butyl peroctoatein 100 parts xylene was added to the reaction mixture over a 45 minuteperiod. The reaction was held at reflux for an additional 2 hours andthen allowed to cool to room temperature to obtain ananhydride-functional polymer having a number average molecular weight of1,900, a polydispersity of 2.1, and a theoretical anhydride equivalentweight of 490.

EXAMPLE 29

A hydroxy-functional polymer was prepared by initially charging apolymerization reactor equipped with a mechanical stirrer, water cooledcondenser, nitrogen inlet, thermometer, heating mantle, and fluidmetering pump, 1,686.9 parts xylene and heated to slightly below reflux(135° C.). A monomer mixture of 967 parts styrene, 322.3 parts methylmethacrylate, 709.1 parts Tone™ M100, 386.8 parts butyl acrylate, 193.4parts hydroxy ethyl acrylate and 252.7 parts t-butyl peroctoate wasmetered into the reaction vessel at a constant rate over a 3 hour timeperiod. The reaction temperature was lowered from 135° C. to 121° C.during the reaction to maintain the temperature at slightly less thanreflux. Temperature was held at 121° C. for an addition 15 minutes afterthe completion of the addition of all monomers. A solution of 2.6 partst-butyl peroctoate in 10.7 parts xylene was added over a 15 minute timeperiod, and the reaction was held at 121° C. for an additional 15 minutetime period. Another solution of 2.6 parts t-butyl peroctoate in 10.7parts xylene was then added over a 15 minute time period, and thereaction was again held at 121° C. for an additional 15 minute timeperiod. A final solution of 2.6 parts t-butyl peroctoate in 10.7 partsxylene was then added over a 15 minute time period, and the reaction washeld at 121° C. for 11/2 hours. A water trap was installed and thereaction was heated to reflux (130° C.) for a 30 minute time period toremove water. The reaction mixture was allowed to cool to roomtemperature and yielded a hydroxy-functional polymer having a numberaverage molecular weight of 3,000, a polydispersity of 3.0, and atheoretical hydroxyl equivalent weight of 691.6.

EXAMPLE 30

A hydroxy-functional polymer was prepared by initially charging apolymerization reactor equipped with a mechanical stirrer, water cooledcondenser, nitrogen inlet, water trap, thermometer, heating mantle,fluid metering pump, 1,264 parts xylene and heated to 138° C. undernitrogen. A monomer mixture of 1,821.6 parts styrene, 1,214.4 partsTone™ M100 and 151.8 parts Vazo 67 was metered into the reaction vesselat a constant rate over a 3 hour time period. The reaction temperaturewas maintained at 138° C. for an additional 15 minutes after thecomplete monomer addition. A solution of 15.9 parts Vazo 67 in 100 partsxylene was then added to the reaction over a 1 hour time period. Thereaction was held for an additional 2 hours and then allowed to cool toroom temperature. The resulting hydroxy-functional polymer had a numberaverage molecular weight of 4,000, a polydispersity of 1.9, and atheoretical hydroxy equivalent weight of 860.

EXAMPLE 31

A clear coating formulation was prepared as follows:

    ______________________________________                                                                   Parts                                              Ingredients                By Weight                                          ______________________________________                                        Hydroxy-Functional Polymer (Example 29)                                                                  206.54                                             Anhydride-Functional Polymer (Example 25)                                                                377.98                                             ERL 4299                   71.43                                              Xylene                     111.09                                             Byk 300                    2.50                                               20% N-Methylimidazole/Methyl Isobutyl Ketone                                                             15.32                                              20% Tinuvin 328/Toluene    23.13                                              Tinuvin 292                2.77                                               ______________________________________                                    

This coating represents approximately 1 hydroxyl group per 2 epoxygroups per 2 anhydride groups. The N-Methylimidazole catalyst waspresent at approximately 1.75% based on anhydride resin solids. Thepresence of all methacrylate monomers and methacrylic acid in theanhydride resin gives less color in the clear formulation than similarformulations with higher acrylate content and/or less acid in theanhydride-functional polymer. This coating was reduced with suitablesolvents and spray applied over a basecoat/primer system coated onBonderite-1000 panels (iron phosphate treatment on cold rolled steel).This coating system was allowed to cure 24 hours under ambientconditions prior to testing.

The cured coating formulation showed only a very light yellow color inthe clearcoat, and exhibited 1 day, 2 and 4 week Konig Pendulum harnessreadings of 10, 30 and 41, respectively. Distinctness of image (DOI) and20 degree gloss values were 87 and 89. The wet adhesion rating(humidity) was 10. Percent gloss retention (humidity) was 92%.

EXAMPLE 32

A clear coating formulation was prepared as follows:

    ______________________________________                                                                   Parts                                              Ingredients                By Weight                                          ______________________________________                                        Hydroxy-Functional Polymer (Example 30)                                                                  211.83                                             Anhydride-Functional Polymer (Example 26)                                                                261.55                                             ERL 4299                   64.63                                              Xylene                     216.93                                             Byk 300                    2.50                                               20% N-Methylimidazole/Methyl Isobutyl Ketone                                                             27.68                                              20% Tinuvin 328/Toluene    23.10                                              Tinuvin 292                2.77                                               ______________________________________                                    

This coating formulation represents approximately 1 hydroxyl group per 2epoxy groups per 2 anhydride groups. The N-Methylimidazole catalyst waspresent at 3.5% based on anhydride solids. This coating was reduced withsuitable solvents and spray applied over a basecoat/primer system coatedon Bonderite-1000 panels (iron phosphate treatment on cold rolledsteel). This coating system was allowed to cure 24 hours under ambientconditions prior to testing.

The cured coating formulation showed slightly more color than thecoating formulation of Example 31. The cured film of this Exampleexhibited a Konig Pendulum Hardness of 10 after one day, 25 after oneweek and 38 after four weeks.

EXAMPLE 33

A clear coating was prepared using the same formulation as in Example 32except that the anhydride resin of Example 13 and the hydroxyl resin ofExample 30 were used. The anhydride-functional vehicle showed a moreyellow color than that of Example 32. The coating was reduced withsuitable solvents and spray applied over a basecoat/primer system oniron phosphate treated cold rolled steel and allowed to ambient cure 24hours before testing.

The resultant film exhibited a Konig Pendulum Hardness of 8 after oneday, 27 after one week and 45 after four weeks, and exhibited excellent20° gloss and distinctness of image.

EXAMPLE 34

A clear coating was prepared as follows:

    ______________________________________                                                                   Parts                                              Ingredients                By Weight                                          ______________________________________                                        Hydroxy-Functional Polymer (Example 30)                                                                  21.27                                              Anhydride-Functional Polymer (Example 27)                                                                28.17                                              ERL 4299                   6.49                                               Xylene                     21.95                                              Byk 300                    0.25                                               20% N-Methylimidazole/Methyl Isobutyl Ketone                                                             2.78                                               20% Tinuvin 328/Toluene    2.32                                               Tinuvin 292                0.28                                               ______________________________________                                    

This coating formulation represents approximately 1 hydroxyl group per 2epoxy groups per 2 anhydride groups. The N-Methylimidazole catalyst waspresent at 3.5% based on anhydride solids. This coating was reduced withsuitable solvents and spray applied over a basecoat/primer system coatedon Bonderite-1000 panels (iron phosphate treatment on cold rolledsteel). This coating system was allowed to cure 24 hours under ambientconditions prior to testing.

This coating formulation showed less color development in theanhydride-functional polymer than in Example 33. The coating exhibited 1day and 2 weeks Konig Pendulum Hardness readings of 9 and 42.

EXAMPLE 35

A clear coating was prepared as follows:

    ______________________________________                                                                   Parts                                              Ingredients                By Weight                                          ______________________________________                                        Hydroxy-Functional Polymer (Example 30)                                                                  213.84                                             Anhydride-Functional Polymer (Example 28)                                                                259.41                                             ERL 4299                   64.38                                              n-Butyl Acetate            221.37                                             Byk 300                    2.50                                               20% N-Methylimidazole/Methyl Isobutyl Ketone                                                             27.60                                              20% Tinuvin 328/Toluene    23.01                                              Tinuvin 292                2.76                                               ______________________________________                                    

This coating formulation represents approximately 1 hydroxyl group per 2epoxy groups per 2 anhydride groups. The N-Methylimidazole catalyst waspresent at 3.5% based on anhydride solids. This coating was reduced withsuitable solvents and spray applied over a basecoat/primer system coatedon Bonderite-1000 panels (iron phosphate treatment on cold rolledsteel).

The anhydride-functional polymer of this Example corresponds toreplacing a small portion of MMA from a high acrylate-anhydride resin(Example 13) with 8.78% methacrylic acid (Example 28) and results in acoating showing improved (less) color, a longer gel time (>12 hoursversus approximately 4 hours) and improved gasohol resistance anddistinctness of image when compared to the coating of Example 33.

While this invention has been described by a specific number ofembodiments, it is obvious that other variations and modifications maybe made without departing from the spirit and scope of the invention asset forth in the appended claims.

The invention claimed is:
 1. In a substrate coated with a multi-layerdecorative and/or protective coating which comprises:(a) a basecoatcomprising a pigmented film-forming polymer; and (b) a transparentclearcoat comprising a film-forming polymer applied to the surface ofthe basecoat composition; the improvement which comprises utilizing asthe clearcoat and/or the basecoat a multicomponent curable compositionwhich is reactive upon mixing of the components, wherein the curablecomposition comprises:(i) an anhydride-functional polymer having anaverage of at least two cyclic carboxylic acid anhydride groups permolecule and wherein the anhydride-functional polymer is the additionpolymerization reaction product of (a) 5 to about 40 weight percent ofan ethylenically unsaturated monoanhydride monomer; and (b) 1 to about15 weight percent of an ethylenically unsaturated carboxylic acidmonomer copolymerizable with the ethylenically unsaturated monoanhydridemonomer; and (c) 45 to about 94 weight percent of at least oneethylenically unsaturated monomer which is copolymerizable with theethylenically unsaturated monoanhydride and ethylenically unsaturatedacid; and (ii) an epoxy-functional compound having an average of atleast two cycloaliphatic epoxy groups per molecule; and (iii) ahydroxy-functional polymer having an average of at least two hydroxylgroups per molecule and comprising the addition polymerization reactionproduct of (a) 10 to about 40 weight percent of a hydroxy-functionalethylenically unsaturated monomer and (b) 60 to about 90 weight percentof at least one ethylenically unsaturated monomer copolymerizable withthe hydroxy-functional monomer.
 2. The coated substrate of claim 1further characterized in that the ethylenically unsaturatedmonoanhydride monomers and the ethylenically unsaturated acid monomersand the ethylenically unsaturated copolymerizable monomers comprise 0 toabout 10 weight percent of the total monomer mixture of acrylatemonomers.
 3. The coated substrate of claim 1 further characterized inthat the ethylenically unsaturated monoanhydride monomers and theethylenically unsaturated acid monomers and the ethylenicallyunsaturated copolymerizable monomers are substantially free of acrylatefunctionality.